Acid- and Metal-Catalyzed Organic Reactions

酸和金属催化的有机反应

• 批准号: RGPIN-2020-03873
• 负责人: Tam, William
• 金额: $ 1.75万
• 依托单位: University of Guelph
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2020
• 资助国家: 加拿大
• 起止时间: 2020-01-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=716694
• 关键词: Acid; Metal; Catalyzed; Organic; Reactions

The discovery and development of new chemical reactions are major foci of research activity in organic chemistry. The reactions and classes of reactions which have found the broadest applicability in organic chemistry are those that address the issues of regio-, stereo- and enantiocontrol and are compatible with a variety of functional groups. Reactions which form multiple bonds, rings and/or stereocenters are particularly important tools for the efficient assembly of complex molecular structures. The long-term objective of our research program is to develop novel synthetic methodologies for the construction of different ring systems, including: nitrogen-containing heterocyclic compounds, spirocyclic compounds, attached-ring compounds and polycyclic compounds. These ring systems are present in many biologically important natural products, which have found use in anti-HIV, anticancer, antiviral and antiretroviral researches. Synthetic methods which allow for the rapid construction of these ring systems with high regio-, stereo- and enantioselectivities would be very useful. Acid and metal-catalyzed reactions are of particular interest due to their ability to control the regio-, stereo- and enantioselectivities by fine-tuning of the metal and surrounding ligands. The use of transition metals in organic synthesis has increased dramatically in the last two decades. Transition metal catalysts provide new opportunities for highly selective reactions that are not achievable by traditional synthetic methods. We will investigate: (i) Ru-catalyzed [2+2] cycloadditions between an alkene and an alkyne; (ii) Ru-catalyzed [3+2] and [3+3] cycloadditions of aziridines; (iii) Acid and metal-mediated reactions of cyclopropanated bicyclic alkenes; and (iv) Synthesis of novel chiral helical organic structures/polymers. During the studies described herein towards the long-term goal, several short-term goals will be accomplished. These short-term objectives include: the development of novel acid and metal-catalyzed reactions, studies on various aspects of these acid and metal-catalyzed reactions, including addressing the questions of reactivity, regio-, stereo- and enantioselectivities, investigation of intramolecular and asymmetric versions of these reactions, and the development of novel metal catalysts and ligands. This research program is important not only in science development but also provides the training for students interested in careers in pharmaceutical and chemical industries.

新化学反应的发现和发展是有机化学研究的主要热点。已发现在有机化学中最广泛适用的反应和反应类别是解决区域控制、立体控制和对映体控制问题并且与各种官能团相容的那些。形成多重键、环和/或立体中心的反应是用于复杂分子结构的有效组装的特别重要的工具。 我们的研究计划的长期目标是开发用于构建不同环系统的新合成方法，包括：含氮杂环化合物，螺环化合物，附环化合物和多环化合物。 这些环系统存在于许多生物学上重要的天然产物中，这些天然产物已被发现用于抗HIV、抗癌、抗病毒和抗逆转录病毒研究。 合成方法，使这些环系统的快速建设与高区域，立体和对映选择性将是非常有用的。 酸和金属催化的反应是特别感兴趣的，因为它们能够通过微调金属和周围的配体来控制区域，立体和对映选择性。 在过去的二十年中，过渡金属在有机合成中的应用急剧增加。过渡金属催化剂为传统合成方法无法实现的高选择性反应提供了新的机会。 我们将调查： (i)Ru催化的烯烃和炔烃之间的[2 + 2]环加成反应; (ii)钌催化的氮杂环丙烷的[3 + 2]和[3 + 3]环加成反应; (iii)环丙烷化双环烯烃的酸和金属介导的反应;以及 (iv)新型手性螺旋有机结构/聚合物的合成。 在本文所述的长期目标研究期间，将实现几个短期目标。 这些短期目标包括：开发新的酸和金属催化反应，研究这些酸和金属催化反应的各个方面，包括解决反应性，区域，立体和对映选择性的问题，这些反应的分子内和不对称版本的调查，以及开发新的金属催化剂和配体。 该研究计划不仅在科学发展方面很重要，而且还为对制药和化学工业职业感兴趣的学生提供培训。